含镓明矾石梯级浸出与综合回收工艺
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摘要
某矿山选铜尾矿经浮选获得的高品位明矾石精矿富含Al、K和Ga等有价金属。为了实现明矾石中有价金属的综合回收,首先采用"焙烧-梯级浸出"工艺选择性浸出Al、K和Ga,再通过冷却结晶与蒸发结晶工艺梯级回收明矾与硫酸铝,最后采用中和法实现Ga富集。结果表明:明矾石精矿经焙烧一段酸浸后,Al、K的浸出率分别为80.31%和87.49%,Ga几乎不浸出;浸出渣经二段酸浸后,Al、Ga和K的浸出率分别为65.67%、86.17%和94.54%。一段酸浸液经冷却结晶后可获得食品级钾明矾纯度达99.65%,结晶后液经蒸发结晶可获得Al_2O_3含量为15.95%的一级硫酸铝产品;利用NaOH控制二段酸浸液的pH为2.5～2.6时,浸出液中Ga沉淀率达98%以上,沉淀物中Ga含量达4100 g/t。XRD分析结果表明,沉淀物经焙烧后,Ga主要以KGa(SO_4)_2的形式存在。
An alunite concentrate is obtained by flotation of copper mine tailings, which is rich in Al, K and Ga and other valuable metals. In order to utilize alunite concentrate comprehensively, firstly a "calcination-cascade leaching" process was proposed to selective leaching of Al, K and Ga. Then, the combination of cooling crystallization and evaporative crystallization processes were adopted to extract alum and aluminum sulfate. Finally, the gallium was enriched by neutralization method. After roasting and one-stage acid leaching, the leaching rates of Al and K after calcining alum stone concentrate are 80.31% and 87.49%, respectively, and gallium can hardly been leached out. At the second-stage acid leaching process, the leaching rates of Al, Ga and K are 65.67%, 86.17% and 94.54%, respectively. After cooling crystallization and evaporative crystallization, a food-grade alum with purity of 99.65% and a firsts aluminum sulfate with Al_2O_3 content of 15.95% are sequently obtained from one-stage livixium. Ga concentrate with content of 1500 g/t is obtained by controlling the pH value of 2.5-2.6 at second-stage lixivium with NaOH, and the precipitation rate of Ga is 98%. XRD analysis results show that the occurrence state of Ga in the sediment after calcination is KGa(SO_4)_2.
An alunite concentrate is obtained by flotation of copper mine tailings, which is rich in Al, K and Ga and other valuable metals. In order to utilize alunite concentrate comprehensively, firstly a "calcination-cascade leaching" process was proposed to selective leaching of Al, K and Ga. Then, the combination of cooling crystallization and evaporative crystallization processes were adopted to extract alum and aluminum sulfate. Finally, the gallium was enriched by neutralization method. After roasting and one-stage acid leaching, the leaching rates of Al and K after calcining alum stone concentrate are 80.31% and 87.49%, respectively, and gallium can hardly been leached out. At the second-stage acid leaching process, the leaching rates of Al, Ga and K are 65.67%, 86.17% and 94.54%, respectively. After cooling crystallization and evaporative crystallization, a food-grade alum with purity of 99.65% and a firsts aluminum sulfate with Al_2O_3 content of 15.95% are sequently obtained from one-stage livixium. Ga concentrate with content of 1500 g/t is obtained by controlling the pH value of 2.5-2.6 at second-stage lixivium with NaOH, and the precipitation rate of Ga is 98%. XRD analysis results show that the occurrence state of Ga in the sediment after calcination is KGa(SO_4)_2.
引文
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[19]韩效钊,徐超,张兴法,王雄,许民才.热分解法综合利用明矾石工艺研究[J].矿冶工程,2002,22(1):72-75.HAN Xiao-zhao,XU Chao,ZHANG Xing-fa,WANG Xiong,XU Min-cai.A process of utilizing alumstone comprehensively by thermal decomposition[J].Mining and Metallurgical Engineering,2002,22(1):72-75.
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[22]周令治,陈少纯.稀散金属提取冶金[M].北京:冶金工业出版社,2008.ZHOU Ling-ye,CHEN Shao-chun.The extraction metallurgy of dissipated metal[M].Beijing:Metallurgical Industry Press,2008.
[23]翟秀静,吕子剑.镓冶金[M].北京:冶金工业出版社,2010.ZHAI Xiu-jing,LüZi-jian.Gallium metallurgy[M].Beijing:Metallurgical Industry Press,2010.
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[2]刘付朋,刘志宏,李玉虎,刘智勇,李启厚.锌粉置换镓锗渣高压酸浸的浸出机理[J].中国有色金属学报,2014,24(4):1091-1098.LIU Fu-peng,LIU Zhi-hong,LI Yu-hu,LIU Zhi-yong,LI Qi-hou.Leaching mechanism of zinc powder replacement residue containing gallium and germanium by high pressure acid leaching[J].The Chinese Journal of Nonferrous Metals,2014,24(4):1091-1098.
[3]张魁芳,曹佐英,肖连生,曾理,张贵清,李青刚.采用HBL121从锌置换渣高浓度硫酸浸出液中萃取回收镓[J].中国有色金属学报,2014,24(9):2400-2409.ZHANG Kui-fang,CAO Zuo-ying,XIAO Lian-sheng,ZENG Li,ZHANG Gui-qing,LI Qing-gang.Extraction of gallium from high concentration sulfuric acid leaching solution of zinc replacing slag by HBL121[J].The Chinese Journal of Nonferrous Metals,2014,24(9):2400-2409.
[4]DUTRIZAC J E,JANBOR J L,CHEN T T.Host minerals for the gallium-germanium ores of the Apex mine,Utah[J].Economic Geology,1986,81(4):946-950.
[5]BAUSTISTA RG.Gallium metal recovery[J].JOM,1989,41(6):30-31.
[6]TORMA A E.Method of extracting gallium and germanium[J].Miner Process Extr Metall,1991(3/4):235-258.
[7]刘延红,郭昭华,池君洲,王永旺,陈东.镓回收方法与技术的研究与进展[J].稀有金属与硬质合金,2016(1):1-8.LIU Yan-hong,GUO Zhao-hua,CHI Jun-zhou,WANGYong-wang,CHEN Dong.Research and the latest development of gallium recovery process and technology[J].Rare Metals and Cemented Carbides,2016(1):1-8.
[8]王晓琳,姬长生,任海兵.我国明矾石资源综合利用现状与发展前景研究[J].中国矿业,2010,19(4):15-17.WANG Xiao-lin,JI Chang-sheng,REN Hai-bing.A study of present situation of comprehensive utilization and development prospect of alunite in China[J].China Mining Magazine,2010,19(4):15-17.
[9]?ZDEMIR M,?ETISLI H.Extraction kinetics of alunite in sulfuric acid and hydrochloric acid[J].Hydrometallurgy,2005,76(3):217-224.
[10]OZDEMIR M,SENGIL I A.Optimum conditions for leaching calcined alunite ore in strong NaOH[J].Canadian Metallurgical Quarterly,1999,38(4):249-255.
[11]HARTM G J,EWING V R.Process for recovering aluminum from alunite.U.S.4230678A[P].1980-10-28.
[12]PAUL R.HERSHMAN.Process of producing aluminate from alunite.U.S.1191105A[P].1916-07-11.
[13]NAZAROV S B,GULAKHMADOV K S,KHAKDODOV M M,AMINOV S G.Processing of aluminum sulfates into alumina[J].Russian Journal of Applied Chemistry,2001,74(8):1392-1394.
[14]MCCULLOUGH W E,DETROIT,MICH.Cyclic process for treating alunite.U.S.2120840[P].1938-06-14.
[15]叶仲屏,孙华,吴红梅,沈帆.明矾石的综合利用[J].化肥工业,2000,27(1):34-36.YE Zhong-bing,SUN Hua,WU Hong-mei,SHEN Fan.Comprehensive utilization of alunite[J].Chemical Fertilizer Industry,2000,27(1):34-36.
[16]王瑞永.明矾石精矿水浸-结晶法制备硫酸钾试验研究[J].有色冶金设计与研究,2014(3):14-16.WANG Rui-yong.Experimental research on water leaching-crystallization process to produce potassium sulfate from alunite concentrate[J].Nonferrous Metals Engineering&Research,2014(3):14-16.
[17]李达,蒋开喜,蒋训雄,汪胜东,范艳青,肖晓阳.明矾石焙砂提取硫酸钾的工艺研究[J].矿冶,2016,25(5):42-45.LI Da,JIANG Kai-xi,JIANG Xun-xiong,WANG Sheng-dong,FANG Yan-qing,XIAO Xiao-yang.Study on the technology of abstracting potassium sulfate from alunite calcine[J].Mining and Metallurgy,2016,25(5):42-45.
[18]张永康,胡四春,张耀,马化龙,冯乃琦.明矾石精矿焙烧-酸浸提取K和Al[J].金属矿山,2017,46(6):104-108.ZHANG Yong-kang,HU Si-chun,ZHANG Yao,MA Hua-long,FENG Nai-qi.Roasting-acid leaching of K and Al from alunite concentrate[J].Metal Mine,2017,46(6):104-108.
[19]韩效钊,徐超,张兴法,王雄,许民才.热分解法综合利用明矾石工艺研究[J].矿冶工程,2002,22(1):72-75.HAN Xiao-zhao,XU Chao,ZHANG Xing-fa,WANG Xiong,XU Min-cai.A process of utilizing alumstone comprehensively by thermal decomposition[J].Mining and Metallurgical Engineering,2002,22(1):72-75.
[20]阮仁满,谭希发,衷水平,伍赠玲,刘晓英.利用热压浸出工艺从明矾石提取氧化铝和硫酸钾.中国,CN101913633A[P].2010-12-31.RUAN Ren-man,TANG Xi-fa,ZHONG Shui-ping,WUZeng-ling,LIU Xiao-ying.Extraction of alumina and potassium sulphate from alunite by thermal pressure leaching.China,CN101913633A[P].2010-12-31.
[21]旷戈,胡松,蔡洋洋,李欢.紫金铜尾矿中明矾石直接加压酸浸[J].中国有色金属学报,2016,26(11):2412-2419.KUANG Ge,HU Song,CAI Yang-yang,LI Huan.Utilizing alunite comprehensively from Zijin copper tailings by directly pressure acid leaching[J].The Chinese Journal of Nonferrous Metals,2016,26(11):2412-2419.
[22]周令治,陈少纯.稀散金属提取冶金[M].北京:冶金工业出版社,2008.ZHOU Ling-ye,CHEN Shao-chun.The extraction metallurgy of dissipated metal[M].Beijing:Metallurgical Industry Press,2008.
[23]翟秀静,吕子剑.镓冶金[M].北京:冶金工业出版社,2010.ZHAI Xiu-jing,LüZi-jian.Gallium metallurgy[M].Beijing:Metallurgical Industry Press,2010.
[24]付培鑫.明矾石利用物理化学原理[M].香港:香港出版社,2005:4-39.FU Pei-xin.Alunite use the laws of physics and chemistry[M].Hong Kong:Hong Kong University Press,2005:4-39.